Hemicyanine dyestuffs

ABSTRACT

The dyestuffs are used for dyeing and printing natural and synthetic materials. Dihydroindoles of the formula   AND THEIR USE AS CONDENSATION COMPONENTS FOR THE MANUFACTURE OF BASIC INDOLENINE DYESTUFFS OF THE FORMULA

"United States Patent [191 Schmitt 1451 Sept. 9, 1975 4] HEMICYANINE DYESTUFFS [75] Inventor: Ernst Schmitt, Cologne, Germany [57] ABSTRACT [73] Assignee: Bayer Aktiengesellschaft, Dlhydromdoles of the formula Leverkusen-Bayerwerk, Germany R 22 Filed: Dec. 9, 1971 2 l A 1.N.:2 ,522 R 1 PP O 06 BQJiCH-CHO l [30] Foreign Application Priority Data Cl'lR Dec. 9, 1970 Germany 2060615 31m, Y 9} [52] US. Cl 260/240.8; 260/240 E; 260/240.6;

260/240.65; 260/240.9; 260/307 F; and their use as condensation components for the 260/326.11; 8/12; 8/54.2; 8/177 R; 8/178 R; manufacture of basic indolenine dyestuffs of the for- 8/ 179 mula [51] Int. Cl C07d 27/56 [58] Field of Search 260/240.8, 240 E R 1 [56] References Cited 2 UNITED STATES PATENTS R X- 3 CH=CH-D 2,077,063 4/1937 Wolff 260/240 E 2,155,459 4/1939 Winter et a1 260/240.8 CHR 2,289,303 7/1942 Dieterle et a1. 260/240 E I 2,906,588 9 1959 Brunkhorst et a1... 260/240.8 CHYR5 3,013,015 12/1961 Plue 260/240 E 3,113,825 12/1963 Streck 260/240 E 3,401,404 9/1968 Seidel et al 260/240 E Primary Examiner-l-Ienry R. .liles Assistant Examiner-S. D. Winters Attorney, Agent, or Firm-Plumley & Tyner The dyestuffs are used for dyeing and printing natural and synthetic materials.

5 Claims, No Drawings HEMICYANINE DYESTUFFS The subject of this invention are dyestuffs of the formula 3 N CH=CH-D wherein R represents a lower alkyl radical and R represents a lower alkyl radical and the radicals R and R together with the shared C atom of the indolenine ring can form a saturated S-membered or 6membered ring,

R represents hydrogen, one or more non-ionic substituents or the remaining part of a fused, optionally nonionically substituted, S-membered or 6- membered ring or representscarboxyl,

R, represents hydrogen or a non-ionic substituent,

R represents hydrogen or anon-ionic substituent,

Y represents halogen,

X represents an anion and D represents the radical wherein 4O R, denotes lower alkyl or an aromatic structure which can be linked to the ring A either directly or via 0, S, NH or N-alkyl,

R denotes hydrogen, aralkyl, alkyl or cycloalkyl and wherein alkyl or cycloalkyl radicals R, can form a S-membered or 6-membered ring with R or with the ring A, optionally via 0, S, NH or N-alkyl, and

R, denotes one or more non-ionic substituents, or

D represents the radical l l H 13 12 wherein R denotes aryl,

R denotes hydrogen or alkyl and either R denotes alkylene linked to R and R denotes hydrogen or R denotes hydrogen, aryl, alkyl or aralkyl and R denotes a single bond to the aryl radical.

A further subject of the invention are mixtures of dyestuffs of the formula III.

The invention also relates to the use of dyestuffs of the formula III for dyeing and printing natural and synthetic materials.

Non-ionic substituents are, for example, alkyl radicals which, according to the invention, can be cyclic or acyclic, branched or straight-chain, substituted or unsubstituted, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, tert.-butyl, cyclohexyl and higher alkyl radicals, such as n-C H and their substitution products, such as chloromethyl, methoxymethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl, nhexyloxymethyl, n-octyloxymethyl, n-nonyloxymethyl, ndodecyloxymethyl, aryloxymethyl, such as phenoxymethyl, p-nitrophenoxymethyl, p-methoxyphenoxymethyl and p-chlorophenoxymethyl, B-chloroethyl, ,B-methoxyethyl, fluorine, chlorine, B-cyanoethyl and also trifluoromethyl, aryl radicals, especially those of the benzene series, such as phenyl, 2-methylphenyl, 3- methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2-chlorophenyl, 4-chlorophenyl, 2-methyl-4- chlorophenyl, 4-cyanopheny], 4-nitrophenyl, 4 methoxyphenyl and 4-methylsu1lphophenyl, aralkyl radicals, especially benzyl and its homologues and their substitution products, such as 4methylbenzyl, 4- chlorobenzyl, 4-nitrobenzyl, 4-methoxybenzyl and 2- phenylethyl, alkoxy radicals, such as methoxy, ethoxy, npropoxy and n-butoxy, sulphamoyl radicals, nitrile groups, carboalkoxy radicals, such as carbomethoxy and carboethoxy, and carboaryloxy radicals, such as carbophenoxy and 4-methylcarbophenoxy, as well as alkenoxymethyl, such as allyloxymethyl, and alkinoxymethyl, such as propargyloxymethyl.

Lower alkyl radicals are those with l 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, nbutyl, isobutyl, tertwbutyl and their substitution products, such as chloromethyl, trifluoromethyl, ,B-chloroethyl, B-methoxyethyl, B-cyanoethyl and ,B-dimethylaminoethyl.

Suitable lower alkenyl radicals are, for example, propen-(2)-yll buten-( 3)-yl-2 and Z-methylene-propyl-l.

Aralkyl radicals according to the invention are, for example, benzyl, ,B-phenylethyl, 'y-phenylpropyl-(2,2)- 4-methylbenzyl, 4-chlorobenzyl. and 4-nitrobenzyl.

Possible anionic radicals A are the organic and inorganic anions which are customary for basic dyestuffs, and as examples there shouldbe mentioned: chloride, bromide, iodide, carbonate, bicarbonate, CH SOf, C H SOf, p-toluenesulphonate, HSOf, S0,, disulphate, aminosulphate, methanesulphonate, benzenesulphonate, p-chlorobenzenesulphonate, phosphomolybdate, phosphotungstate, acetate, benzoate, chloroacetate, formate, propionate, lactate, crotonate, N0 perchlorate, ZnCl the anions of saturated or unsaturated aliphatic dicarboxylic acids, such as malonic acid, maleic acid, tartaric acid, citric acid, oxalic acid, itaconic acid, succinic acid, glutan'c acid, adipic acid, pimelic acid and suberic acid, and alkanesulphonic acid radicals, such as ndodecylsulphonic acid,

tetrapropylenesulphonic acids, C -C- alkanesulphonic acid mixtures and ligninsulphonic acids.

Colourless anions are preferred; for dyeing from an aqueous medium, those anions are preferred which do not excessively impair the solubility of the dyestuff in water.

For dyeing from organic solvents, those anions are also frequently preferred which promote the solubility of the dyestuff in organic solvents or at least do not affect it adversely, such as anions of monobasic organic acids with 4 30 carbon atoms.

Dyestuffs of the formula III are manufactured by condensing compounds of the formula l-l D (Vlll) with compounds of the formula 3 CH-CHO I FER ;v

. CHR Y' in the presence of acid condensation agentsfln the above formulae II and VIII, D, R, R R R R and Y have the same meaning as given above in formula III.

Within the framework of the compounds of the formula ll, those of the formula IV are particularly preferred:

v I R v 2 3 N CH-CHO c'mn (Iv) 4 CHClR wherein R represents methyl, ethyl, or n-propyl,

R represents methyl, ethyl or n-propyl,

R represents hydrogen, one or more identical or different radicals methyl, ethyl, n-propyl, tert.butyl, n-hexyl, n-dodecyl, cyclohexy], fluorine, chlorine, phenyl, 4-nitrophenyl, 4-methoxyphenyl, benzyl, trifluoromethyl, nitrile, carboxy, methylmercapto, ethylmercapto, methylsulphonyl, acetamino, methoxy, ethoxy, n-propoxy, n-butoxy, phenoxy, carbomethoxy, carboethoxy, carbophenoxy or sulphamoyl, and

R and R independently of one another represent hydrogen, methyl, ethyl, n-propyl, n-butyl, npentyl, n-hexyl, n-nonyl, carbophenoxy, methoxymethyl, ethoxymethyl, n-propoxymethyl, nbutoxymethyl, n-hexyloxymethyl, n-' octyloxymethyl, n-nonyloxymethyl, ndecyloxymethyl, n-dodecyloxymethyl, phenoxywherein methyl, p-nitrophenoxymethyl, p-methoxyphenoxthe radicals R and R or R and R represent hydrogen, or one of the radicals R and R or R and R represents hydrogen and the other represents methyl. For economic reasons, those compounds of the formulae II and IV are of outstanding importance, wherein R and R or R and R represent hydrogen. Compounds of the formula ll can be manufactured by reaction of 9a-methyl-2,3,9,9a-tetrahydro-oxazolo- [3,2a]-indoles of the formula R I R2 3 on, (I)

I R,CHCHR,-,

wherein R represents a lower alkyl radical and R represents a lower alkyl radical and the radicals R and R, can form a saturated S-membered or 6- membered ring with the shared C atom of the 2,3- dihydroindole' ring,

R represents hydrogen, oneor more non-ionic substituents or the remaining part of a fused, optionally non-ionically substituted S-membered or 6- membered ring orrepresents carboxyl,

R represents hydrogen or a non-ionic substituent and R denotes hydrogen or a non-ionic substituent, with formamides of the formula 0 R H H CN (Vl) wherein R represents hydrogen or an alkyl radical and- R represents an alkyl, aralkyl or aryl radical, in the presence of acid halides.

Compounds ofthe formula IV and of the groups which have been singled out can be manufactured in the same manner.

When using mixtures of 9a-methyl-2,3,9,9a-tetrahydrooxazolo-[3,2al-indoles which can arise in the preparation of unsymmetrical oxiranes, mixtures of compounds of the formula II are produced.

Within the framework of the formamides to be used according to the invention, those are preferred wherein R represents alkyl radicals with l 5 carbon atoms and R represents alkyl radicals with l 5 carbon atoms and radicals of the benzene series, such as phenyl,

Z-methylphenyl, 4-methylphenyl, 2,4-

dimethylphenyl, 2-chlorophenyl, 4-chloropheny1,

2methyl-4-chlorophenyl and 4-nitrophenyl.

The reaction can be carried out in a diluent. Possible diluents of this nature are, especially, acetonitrile, propionitrile, benzonitrile, nitromethane, Z-nitropropane and chlorobenzene. Within the range of the diluents, acetonitrile is particularly preferred.

The reaction of 9a-methyl-2,3,9,9a-tetrahydrooxazolo[3,2a]-indoles to give l-(2-halogenalkyl)-2- (formylmethylene )-3 ,3-dimethyl'2,3-dihydroindoles can be carried out by introducing the compounds of the formula II into reaction mixtures of acid halides and a formamide, for example dissolved in acetonitrile. The reaction can also be carried out in an excess of formamide, without further diluent.

Acid halides which are suitable according to the invention are, for example, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide, phosgene, thionyl chloride and benzoyl chloride. Acid chlorides, especially phosphorus oxychloride and phosgene, are preferred.

The reaction temperature is between and 120C, preferably between and 65C. The reaction is frequently already complete after 2 hours. At times it can, however, be necessary to extend the reaction time to 25 hours.

Formamides which are suitable according to the in vention are, for example: N-methylformamide, N- ethylformamide, N-n-propylformamide, N-isobutylformamide, N,N-dimethylformamide, N-methyl-N-ethylformamide, N-diethylformamide, N-methyl-n-propylformamide and N-phenyl'N- methylformamide. N,N-Dimethylformamide is .preferred.

As 9a-methyl-2,3,9,9a-tetrahydro-oxazolo-[3,221]- indole starting materials, the following can in particular he used: 9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo- [3,2a]-indole, 7,9,9,9a-tetramethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-chloro-9,9,9a-trimethyl- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7-methoxy- 9,9,9atrimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole, 7-ethyl-9,9,9a-trimethyl-2,3,9,9atetrahydrooxazolo-[3,2a]-indole, 7 cyclohexyl-9,9,9a-trimethyl- 2,3,9,9atetrahydro-oxazolo-[3,2a]-indole, 7- trifluoromethyl-9,9,9a-trimethyl2,3,9,9a tetrahydrooxazolo-[3,2a]indole, 7-acetamino-9,9,9a-trimethyl- 2,3,9,9a-tetrahydro-oxazolo-[3,2al-indole, 7- cyclohexyl-S,9,9,9a-tetramethyl-2,3,9,9a-tetrahydrooxazolo-[3 2a]-indole, 9,9diethyl-9a-methyl2,3,9,9atetrahydro-oxazolo-[ 3,2a]-indole, 9,9diethyl-7,9adimethyl-2,3,9,9a-tetrahydro-oxa2olo-[3,2a]-ind0le, 9,9-diethyl-7-chloro-9a-methyl2,3,9,9atetrahydrooxazolo-[3,2a]-indole, 2,9,9,9a-tetramcthyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole, 3,9,9,9atetramethyl2,3,9,9a-tetrahydro-oxazolo-[3,221]- indole, 9,9,9a-trimethyl-2-phenoxy-2,3,9,9atetrahydro-oxazolo-[ 3 ,2a]-indole, 9,9,9a4rimethyl-2- phenoxymethylene-2,3,9,9a-tetrahydro-oxazolo- [3,2a]-indole, 9,9,9a-trimethyl-7-methoxy'2- phenoxymethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2 a]- indole, 9,9-diethyl-9a-methyl-2-phenoxymethyl- 2,3,9,9a-tetrahydro-oxazolo-3,2a]-indole, 9,9,9atrimethyl-Z-Chloromethyl-2,3,9,9a-tetrahydro-oxazolo- [3,2a]-indole, 6-chloro9,9,9a-trimethyl-2,3,9,9a' tetrahydro-oxazolo-[3,2a]-indole, 5-chloro-9,9,9atrimethyl-2,3 ,9,9a-tetrahydro-oxazolo-[ 3,2a]-indole, 7-fluoro-9 ,9 ,9atrimethyl-2 ,3 ,9 ,9 a-tetrahydro-oxazolo- [3,2a]indole, 7-chloro6-fluoro-9,9,9a-trimethyl- 2,3,9,9a-tetrahydro-oxazolo-[l3,2a]-indole, 7-chloro-2- phenoxymethyl-9,9,9a'trimethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole, 7,9,9,9a-tetramethyl-2- phenoxymethyl-2,3 ,9,9a-tetrahydro-oxazolo- 3 ,2a] indole, 7-carboxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 7'carboxy-2- phenoxymethyl-9,9,9a-trimethyl-2,3,9,9atetrahydrooxazolo-[3,2a]-indole, 7-carboxy3-phenoxymethyl- 9 ,9 ,9a-.trimethyl-2,3 ,9,9atetrahydro-oxazolo- 3 ,2a indole, 7-ethoxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a]-indole, 9,9,9a-trimethyl-2- ethoxymethyl-2,3,9,9a-tetrahydro-oxazolo- 3 ,2a]- indole, .9,9,9atrimeth.yl-2-(n-propoxymethyl)- 2,3,9,9a:tetrahydro-oxazolo-[3,2a]-indole, 9,9,9atn'methyl-2-( n-hexyloxymethyl )-2,3 ,9,9a*tetrahydrooxazolo-[.3,2a]-indole, 9,9,9a-trimethyl-2 methoxymethyl2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole, 9,9,9a-trimethyl-3-methoxymethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole, 7,9,9,9atetramethyl-Z-phenoxymethy]-2,3,9,9a-tetrahydrooxazolo[3,2a]-indole, 7-fluoro-9,9,9a-trimethyl-2- phenoxymethyl-2,3 ,9,9a-tetrahydro-oxazolo- 3,2a]- indole, 7-chloro-9,9,9a-trimethyl-2-methoxymethyl- 2,3,9,9atetrahydro-oxazolo-[3,2a]-indole, 7-chloro- 9,9,9a-trimethyl2-ethoxymethyl-2,3,9,9a-tetrahydrooxazolo-[3,2a] -indole, 7-chloro-9,9,9a-trimethyl-2-(nhexyloxymethyl)-2,3,9,9a-tetrahydro-oxazolo-[3,2a]- indole, 7-chloro-9,9,9a-trimethyl-2-(npropoxymethyl)-2,3,9,9a-tetrahydro-oxazolo-[3,221]- indole, 7-chloro-2,9,9,9a-tetramethyl-2,3,9,9a-tetrahy dro-oxazolo-[3,2a]-indole, 7-chloro-3,9,9,9atetramethyl-2,3 ,9,9a-tetrahydro-oxazolo-[ 3 ,2a]- indole, 9,9,9a-trimethyl3 -chloromethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole, 9,9,9a-trimethyl-2- ethyl-2,3,9,9a tetrahydro-oxazolo-[3,2a]-indole, 9,9,9- a-trimethyl-7-phthalimidomethyl-2,3,9,9a-tetrahydrooxa2olo-[ 3 ,2a]-indole, 9,9,9a-trimethyl-7-cyano- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole, 2,9,9,9atetramethylJ-cyano-Z,3,9,9a-tetrahydro-oxazolo- [3,2a]-indole, v2,3,9,9,9a-pentamethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]-indole, 9,9,9a-trimethyl-7- cyano-2-phenoxymethyl-2,3,9,9a-tetrahydro-oxazolo- [3,2a]-indole, 5,6-benzo-9,9,9a-trimethyl-2,3,9,9atetrahydro-oxazolo-[3,2a]indole, 6,7-benzo-9,9,9atrimethyl-2,3 ,9, a-tetrahydro-oxazolo-[ 3 ,2a]-indole, 2,9,9,9a-tetramethyl7-cyclohexyl-2,3,9,9a-tetrahydrooxazolo-{3,2a]-indole and 3,9,9,9a-tetramethyl-7- cyclohexyl-Z ,3 ,9,9a-tetrahydro-oxazolo-[ 3 ,2a -indole.

The above mentioned 9a-methyl-2,3,9,9a-tetrahydro-oxazolo[3,2al-indoles of the formula are prepared by alkylating an indolenine of the formula condensation reactions for the manufacture of basic dyestuffs. R1 A preferred group amongst the dyestuffs of the formula III are those of the formula R 2 (I 3 N CH a 1 Efi 2 R3 R2 X" with oxiranes of the formula N H=CH R represents methyl, ethyl or n-propyl,

R represents methyl, ethyl or n-propyl,

R represents hydrogen or one or more identical or different radicals from amongst methyl, ethyl, npropyl, tert.-butyl, n-hexyl, n-dodecyl, cyclohexyl, fluorine, chlorine, phenyl, 4-nitrophenyl, 4- methoxyphenyl, benzyl, trifluoromethyl, nitrile, carboxyl, methylmercapto, ethylmercapto, methylsulphonyl, acetamino, methoxy, ethoxy, npropoxy, n-butoxy, phenoxy, carbophenoxy, allyloxy or sulphamoyl and D, R.,, R and X have the abovementioned meaning.

Within the framework of the dyestuffs of the formula V, preferred dyestuffs are those of the formula v y CrIClR J in which R R R R and R have the meaning given above.

The reaction can be carried out in bulk or in the presence of substances which react acid or alkaline, with or without the addition of water. Instead of water, organic solvents can also be used; at times it is useful to use a mixture of water and one or more organic solvents.

Organic acids which are suitable in the preparation of the starting materials of the formula (I) are, for example, formic acid, acetic acid, propionic acid, monochloroacetic and dichloroacetic acid, B-chloropropionic acid, succinic acid, benzoic acid and p-toluene-sulphonic acid. Organic and inorganic acids can also be used as mixtures; in this case, aqueous hydroh i 22 g ;e gflztfgfifa lgfuiggis acld and phosphor: R R R R and X have the abovementioned Possible substances which give an acid reaction are also Lewis acids, such as ZnCl sncn, AlCl BF, and represents hydrogen methyl ethyl P FeCl which are preferably used together with organic t x ,mdodecyl fluorme acids, for example those from post sulphonated chlorine, trifluoromethyl, nltrlle, carboxyl, methylstyrenedivinylbenzene copolymersi mercapto, ethylmercapto, methylsulphonyl, As organic solvents, the following can, for example, acetammo Carbomethoxy carboethoxy sulpha' be used: methanol, ethanol, ethylene glycol, benzyl almoyl mahylmenfapto ethylmercapto methylsulcohol, acetone, isopropyl methyl ketone, methyl ethyl 5O h acetammo cyclohexyl phenyl 4' ketone, cyclohexanol, tetrahydrofurane, dioxane, ethyl mtrophenyl methoxy ethoxy n'propoxy Wbutoxy meaning,

acetate, phthalic acid diethyl ester, phthalic acid nor phenoxy propyl ester, cyclohexane, cyclohexene, benzene, xy- R6 represents methyl, ethyl, 'P PY y lenes, chlorobenzene or ethylene chloride. B' y y Bchloroethyl, B' y y y The reaction is preferably carried out in acetic acid Qmethoxyethyl, and particuarly preferably in acetic acid-water mixrepresents hydrogen, methyl, ethyl, n pr0py1, tures butyl, B-cyanoethyl, B-chloroethyl, B-hydroxy- The reaction can be carried out at temperatures beethyl, bumahoxyethyl, cyclohexyl or mettwlcytween about and 'HSOOQ Preferably at p clohexyl or the radicals R and R together with tures between 25 and 80C. Especially in the case of the Natom f a piperidinea morpholine, i low-boiling oxiranes, such as ethylene oxide, propylene zine or thiazine ring, and

oxide, butylene-( 1,2) oxide and l-chloro-2,3- epoxypropane, the reaction can advantageously be carried out under pressure.

It has now been found that compounds of the formula II or of the formulae which have been singled out are, urprisingly uitable for use as aldehyde components in Further preferred dyStUffS are those Of the formula R represents hydrogen or one or more identical or different chlorine, bromine, methyl, ethyl, n-

propyl, nitrile, methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy radicals.

in which R,, R R R R and X have the abovementioned meaning and R represents an aromatic radical which can be linked to the ring A" directly or via 0, S, N-alkyl or N-aralkyl or via a methylene group and R represents hydrogen, methyl methyl and R represents hydrogen or one or more fluorine,

chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, n-butyl, methoxy, ethoxy, n-propoxy, acetamino or nitrile radicals. Further dyestuffs to be highlighted from amongst those of the formula V are those of the formula wherein R,, R R R R and X have the abovementioned meaning,

R represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, cyanoethyl, B-chloroethyl, fi-methoxyethyl or B-ethoxyethyl,

R represents hydrogen or one or more identical or different radicals from amongst fluorine, chlorine, methyl, ethyl, n-propyl, nitrile, methoxy, ethoxy, n-propoxy, isopropoxy or n-butoxy, and

Z represents a single bond, an O atom or S atom, a

methylene group or an ethylidene group, or N- CH N-C H,-,, N-n-C H or N-n-C H,,,

R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl or cyclohexyl and R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl or cyclohexyl and R and R together can form a S-membered or 6- membered ring and represent a trimethylene or tetramethylene bridge which is optionally substituted by methyl, ethyl, n-propyl, methoxy or ethoxy.

Amongst the dyestuffs of the formula Vc, those in which Z represents a single bond should be particularly singled out. A further preferred group within the framework of the dyestuffs of the formula V corresponds to the formula A further preferred group amongst the dyestuffs of the formula V in which the radical D represents are those of the formula in which I R R R R R and X have the abovementioned meaning and I R represents hydrogen or one-or more identical or different radicals from amongst chlorine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert.-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, amino, acetamino, n-propionylamino, dimethylamino, diethylamino or di-(B-hydroxyethyl)-amino,

R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl or cyclohexyl and R represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl and cyclohexyl, or

R and R conjointly form a S-membered or 6- membered ring and represent a trimethylene or tetramethylene bridge which is optionally substituted by methyl, ethyl, n-propyl, methoxy or ethoxy and Z represents a single bond, or S, a methylene or ethylidene group, NH, N-CH N-C H N- n-C H or N-n-C,H,,. A preferred group amongst the dyestuffs of the formula V in which D represents the radical C I T RH id l3 12 are those of the formula R2 I m R12 I 3 n CH=CH N x (Vlla) l CHR, R

and X have the abovemenn-propyl,

R R R R R and X have the abovementioned meaning, I g I R represents methyl, ethyl or S-chlorobutyl and R represents hydrogen orpne or more identical or different radicals from amongst chlorine, fluorine, trifluoromethyl, methyl, ethyl, n-propyl, iso-propyl,

, n-butyl, tert.-butyl, methoxy, ethoxy, carboxyl, carbomethoxy, carboethoxy, acetamino, nitrile or nitro In place of the aldehydes of the formula ll, their functionally equivalent derivatives can also be employed, such as the primary products of the Vilsmeier reaction, Schiffs bases, azomethines, oximes, nitrones or hydrazones, which furthermore are obtainable from the corresponding aldehydes analogously to known processes.

The dyestuffs of the formulae Va, b and c as well as Vlla and Vllb are obtained if compounds of the formula R 9 R I 2 5 fi t-c" H-CHO (Il I 3 4 CHClR in which R R R R and R have the abovementioned meaning, are reacted with compounds of the formulae R. H N (lXa) \R,'

-N (IXb) H I v i i I H R H 5 (lXc) -Continued Tlii I l-l H- =C-N (X21) z II R12 L R, R

wherein in the presence of acid condensation agents, in accordance with known methods. Suitable condensation agents are, for example, formic acid, acetic acid, propionic acid, acetic anhydride, propionic anhydride, sulphuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, phosphorus oxychloride, phosphorus pentoxidc, thionyl chloride, AlCl ZnCl BF PCl PCL, or mixtures thereof. The reaction can also be carried out in the presence of water or of organic solvents such as benzene, toluene, xylene, acetonitrile, propionitrile, chlorobenzene, dichlorobenzene, methanol, ethanol, n-propanol, iso-propanol, n-butanol or isobutanol.

.A preferred embodiment is the condensation in glacial acetic acid, in aqueous sulphuric acid, in aqueous hydrochloric acid or with the further addition of zinc chloride.

Dyestuffs of the formulae Vla and b are obtained if compounds of the formula I R R 5 N "CH-CHO (IIa) 3HR R C C in which R,', R R R and R have the abovementioned meaning, are reacted with compounds of the formula R R R R R and Z have the abovementioned meaning,

in the presence of acid condensation agents, in accordance with known methods. Suitable agents for this purpose are, for example: formic acid, acetic acid, propionic acid, sulphuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, acetic anhydride, propionic anhydride, ZnCl or ER, or mixtures thereof. The reaction can also be carried out in the presence of water or of organic solvents. Condensations in the absence of water should be singled out. In particular, the condensations with compounds of the formulae Xla and Xlb are carried out in glacial acetic acid.

Suitable components according to the formula II for the manufacture of dyestuffs according to the invention are, for example, the: l-(2'-chloroalkyl)-2- formylmethylene-3,3-dialkyl-2,3-dihydroindoles which are obtained from the oxazolo[3,2a]-indoles which have been listed.

Suitable components according to the formula lXa are: N,N-dimethyl-aniline, N-methyl-N-ethyl-aniline, N,N-diethylaniline, N,N-di-n-propyl-aniline, N-methyl- N-( n )-propyl-aniline, N,N-di-n-butyl-aniline, N- methyl-N-B-hydroxyethyl-aniline, N-ethyl-N-B-hydroxyethyl-aniline, N-methyl-N-B-chloroethylaniline, N- ethyl-N-B-chloroethyl-aniline, N,N-di-B- hydroxyethylaniline, N,N-di-B-chloroethyl-aniline, N- methyl-N-B-cyanoethylaniline, N-ethyl-N-B-cyanoethyl-aniline, N-methyl-N-Bwyanoethyl-3-methyl-aniline, N-methyl-N-cyclohexyl-aniline, N-ethyl-N-B- chloroethyl-3-methyl-aniline, N-butyl-N-B-chloroethyl-aniline, N-butyl-N-B-hydroxyethyl-aniline, Nethyl- N-(2'-dimethylaminoethyl)-aniline, N,N-dimethyl-otoluidine, N,N-dimethyl-m-toluidine, N-ethyl-N-B- hydroxyethyl-m-toluidine, N-ethyl-N-benzyl-aniline, N-phenyl-morpholine, N-phenyl-piperidine, N,N'di- (2 ,3 -dihydroxypropyl )-aniline, N,N-dimethyl-3- chloroaniline, N,N-dimethyl-3-nitro-aniline, N,N- dibenzyl-aniline, N,N-dibenzyl-m-toluidine, l-dimethylamino-naphthalene, 3-N,N-dimethylaminoacetanilide, 3-N,N-diethylamino-phenetol and 1-phenyl-4-methyl-piperazine.

Suitable components according to the formula IXb are: diphenylamine, 4-methyldiphenylamine, 4- chlorodiphenylamine, 4-metlhoxydiphenylamine, 4- ethoxydiphenylamine, N-methyldiphenylamine, N- methyl-4chlorodiphenylamine, N-methyl-4- methoxydiphenylamine, N-methyl-4- ethoxydiphenylamine, N-methyl- 4methyldiphenylamine, N-ethyldiphenylamine, N- ethyl-4-chlorodiphenylamine, N-ethyl-4- methoxydiphenylamine, N-ethyl-4- ethoxydiphenylamine, N-ethyl-4-ethoxy3 methyldiphenylamine, N-methyl-4-ethoxy-2- methyldiphenylamine, 2-nitro-4-methyldiphenylamine, N-methylcarbazole, N-ethylcarbazole, N-(n)-propylcarba2ole, N-(n)-butylcarbazole, N-isobutylcarbazole, 3-acetamino-9-methylcarbazole, 9,10- dihydroacridine, phenothiazine, phenoxazine, phenazine, Z-methylphenoxazine, 3-nitrocarbazole, 3- acetylamino-9-methylcarbazole, 3-acetylamino-9- ethylcarbazole, 3-acetylamino-9-(n)-propylcarbazole, 3-propionylamino-9-ethylcarbazole and 3- benzoylamino-9-ethylcarbazole.

As components according to the formula lXc, there may be mentioned: l-methyll ,2,3 ,4- tetrahydroq uinoline, l-ethyl- 1 ,2,3,4- tetrahydroquinoline, l,2-dimethyl-2,3-dihydroindole, l-ethyl-2-methyl-2,3-dihydroindole, 1,23,3- tetramethyl-Z,3-dihydroindole, l,2,3.3-tetramethyl-6- chloro-2,B-dihydroindole, 1,2,3 ,3-tetramethyl-7- chloro-2,3-dihydroindole, l-ethyl- 2,3,3-trimethyl 2,3- dihydroindole, l-ethyl-2,3,3-trimethyl- 6-chloro-2,3-dihydroindole, 1,2-dimethyl3,3-diethyl- 2,3-dihydroindole, tetramethyl-quinoxaline, l,2,3,4-tetrahydro-l ,2,3,4 tetramethyl-o-methoxy-quinoxaline, l,2,3,4,4a,9ahexahydro-9-methylcarbazole, 1,2,3,4,4a-hexahydro- 9-ethylcarbazole, 1,2,3,4-tetrahydro-l ,4-dimethyl quinoxaline and l ,2,3,4-tetrahydro-2,3-dimethyl-1,4- diethylquinoxaline.

Suitable components according to the formula Xa are: indole, 2-phenylindole, l-methyl-2-phenylindole, 1-ethyl-2-phenylindole, l-cyanoethyl-2-phenylindole, l-methyl-5-methoxy-2- phenylindole, l-methyl-5-chloroindole, 1,5-dimethyl- Z-phenylindole, 2-methyl-7-ethylindole, 2-methyl-7- iso-propylindole, 5-nitro-2-methyl-7-ethylindole, 7 ethyl-2-phenylindole, l-ethyl-2-methyl-6,7- benzoindole, 2,5-dimethylindole, 1,2-dimethylindole, Z-methylindole, l-B-ehloroethylindole, l-B-chloroethyl-2-methylindole, l-,8-chloroethyl-2-phenylindole, l-[3cyanoethyl-2-methylindole and 2-(4-chlorophenyl)-7-ethylind0le.

The following can be used as starting components according to the formula Xb for the manufacture of dyestuffs of the formula VIIb: 1,3,3-trimethyl-2- methylene-2,3-dihydroindole, l-methyl-3,3-diethyl-2- methylene-2,3-dihydroindole, 1,3 ,3-triethyl-2- methylene-2,3-dihydroindole, 1,3,3-trimethyl-5- chloro-2-methylene-2,3-dihydroindole, 1 ,3,3,5- tetramethyl-2-methylene-2,3-dihydroindole, 1 ,3 ,3- trimethyl-5-methoxy-2-methylene-2,3-dihydroindole,

l ,3,3-trimethyl-5-nitro- 2-methylene-2,3-dihydroindole, acetylamino-2-methylene-2,3-dihydroindole, trimethyl-S-phthalimido-methyl-Z-methylene-2,3- dihydroindole, 1,3,3-trimethyl-5-ethoxy- 2-methylene-2,3-dihydroindole. trifluoromethyl-2-methylene-2,3-dihydroindole, 1,3,3- trimethyl-S-carbomethoxy- 2-methylene-2,3- dihydroindole, 1,3,3-trimethyl-5-ethyl-2- methylene2,3-dihydroindole, 1,3,3-trimethyl-5- carboethoxy-2-methylene-2,3-dihydroindole, 1,3,3- trimethyl-5-carboxy-2-methylene-2,3-dihydroindole and l,3,3-trimethyl-5-fluoro-2-methylene-2,3- dihydroindole.

Suitable components according to the formula Xla are: p-anisidine, m-anisidine, ptoluidine, m-toluidine, 4-ethylaniline, 4-butoxy-aniline, p-phenetidine, 4-isopropyl-aniline, 4-(n)-propyl-aniline, 4-tcrt.-butyl- 1,3,3-trimethyl-5- 1,3,3-

l,2,3,4-tetrahydro-1,2,3,4.

l-(n)-propyl-2-phenylindole,

1,3,3-trimethyl-5- aniline, N-methyl-aniline, aniline, 4-chloro-aniline, 4- (n)-butyl-aniline, 4-iso-butylaniline, 4-dodecyl-aniline, 4-(n)-propoxy-aniline, 4-isopropoxy-aniline, 4-benzylaniline, 4-methoxy-N-methyl-aniline, 4-methoxy-N- ethyl-aniline, 4-fluoro-aniline, 4-methyl-N-ethylaniline, 4-methyl-N-methyl-aniline, 3,4-dimethyl-aniline, 2,4- dimethyl-aniline, 3-chloro-aniline, 2-chloro-N- ethylaniline, 2,6-dichloro-aniline, 3,5-dichloro-aniline, 3-nitroaniline, 4-chloro-3-methyl-aniline, 3chloro-4- methyl-aniline and 2,5-dimethyl-aniline.

Suitable components according to the formula Xlb are: 2-methyl-2,3-dihydroindole, 2-methyl'7-ethyl-2,3- dihydroindole, 2,3-dimethyl-2,3-dihydroindole, 2- ethyl-3-methyl-2,S-dihydroindole, 2,3,5-trimethyl-2,3- dihydroindole, 5-methoxy-2,3-dimethyl- 2,3-dihydroindole, 1,2,3,4,4a,9a-hexahydro-carbazole, l ,2,3,4,4a,9a-hexahydro-6-dimethylamino-carbazole, l,2,3,4-tetrahydro-2,3-dimethyl-quinoxaline, 1,2,3,4- tetrahydro-quinoxaline, 1 ,2,3,4tetrahydro-2,3,4-' trimethyl-quinoxaline, 1,2,3,4-tetrahydro-2,3- dimethyl-o-methoxy-quinoxaline, l,2,3,4-tetrahydro- 2,3-dimethyl-4-ethyl-quinoxaline, l,2,3,4-tetrahydroquinoline, -methoxyl ,2,3,4-tetrahydro-quinoline, l,2,3,4,4a, 9a-hexahydro-phenazine and 1,2,3,4,4a,9ahexahydrophenoxazine.

If mixtures of compounds of the formula Ila are used, mixtures of dyestuff of one of the formulae Va, b and c; Vla and b; VIla and VIIb are obtained.

The new products are valuable dyestuffs which can be used for dyeing and printing materials of leather, tannin-treated cotton, cellulose, synthetic polyamides and polyurethanes, and for dyeing lignin-containing fibres, such as coir, jute and sisal. They are furthermore suitable for the manufacture of writing fluids, rubberstamp inks and ball pen pastes and can also be used in flexographic printing.

Suitable material for dyeing with the basic dyestuffs of the above general formulae III, V, Va, b, c, Vla, b, VIIa and b are, in particular, flocks, fibres, filaments, tapes, woven fabrics or knitted fabrics of polyacrylonitrile or of copolymers of acrylonitrile with other vinyl compounds, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinylpyridine, vinylimidazole and vinyl alcohol, acrylic and methacrylic acid esters and amides, and asymmetrical dicyanoethylene, or flocks, fibres, filaments, tapes, woven fabrics or knitted fabrics of acid-modified aromatic polyesters and acidmodified polyamide fibres. Acid-modified aromatic polyesters are, for example, polycondensation products of sulphoterephthalic acid and ethylene glycol, that is to say polyethyleneglycolterephthalates containing sulphonic acid groups (type DACRON 64 of El. DuPont de Nemours and Company), such as are described in Belgian Patent Specification No. 549,179 and US. Pat. No. 2,893,816.

Dyeing can be effected from a weakly acid liquor, the goods appropriately being introduced into the dyebath at 40 60C and then being dyed at the boil, It is also possible to dye under pressure at temperatures above C. Furthermore, the dyestuffs can be added to spinning solutions for the manufacture of fibres containing polyacrylonitrile, or can be applied to the unstretched fibre.

The dyeings of the dyestuffs according to the invention, of the formulae Ill, V, Va, b, c, Vla, b, Vlla and b, on materials of polyacrylonitrile or acid-modified polyester fibres are distinguished by very good fastness to light, wet processing, rubbing and sublimation and by a high affinity to the fibre. The dyestuffs form lightfast pigments with anionic precipitants, such as alu mina, tannin and phosphotungstic acids or phosphomolybdic acids, which can be used advantageously in paper printing.

The dyestuffs can be used individually or as mixtures. They are very suitable for dyeing mouldings of polymers or copolymers of acrylonitrile or asymmetrical dicyanoethylene, acid-modified aromatic polyesters or acid-modified synthetic polyamides, in chlorinated hydrocarbons as the dyebath, provided they carry substituents, such for example, the tert.-butyl group, which assist the solubility in chlorinated hydrocarbons, or the amine X in the formulae Ill, V, Va, b, c, Vla, b, VIla and b is the anion of a monobasic organic acid with 4 30 carbon atoms.

Such organic acids are, for example: Z-ethylcaproic acid, lauric acid, oleic acid, linoleic acid, a mixture of aliphatic carboxylic acids with 15 19 carbon atoms (Versatic Acid l5 l9), a mixture of aliphatic carboxylic acids with 9 1 1 carbon atoms (Versatic Acid 91 l coconut fatty acid first runnings, tetradecanoic acid, undecylenoic acid, dimethylpropanoic acid, dimethylacetic acid, carboxylic acids of which the hydrocarbon chain is interrupted by hetero-atoms, such as nonylphenoltetraethylene-glycol-ether-propionic acid, nonylphenoldiethylene-glycol-ether-propionic acid, dodecyltetraethyleneglycol-ether-propionic acid, 3-(nonyloxy)- propionic acid. 3-(isotridecyloxy)-propionic acid, 3- (isotridecyloxy )-diethylene-glycol-ether-propionic acid, ether-propionic acid from the alcohol mixture with 6 10 carbon atoms, nonylphenoxyacetic acid, aromatic carboxylic acids, such as tertbutylbenzoic acid, cycloaliphatic carboxylic acids, such as hexahydrobenzoic acid, cyclohexenecarboxylic acid, abietic acid and sulphonic acids, such as tetrapropylenebenzenesulphonic acid.

Dyestuffs of the abovementioned formulae in which the anion A is the anion of one of the acids listed here are particularly preferred.

If the dyestuffs according to the invention are in the form of salts of the monobasic organic acids with 4 30 carbon atoms with have been mentioned, concentrated solutions, of good stability, of these dyestuffs in chlorinated hydrocarbons can be manufactured, where appropriate with the addition of polar organic solvents which are completely miscible with chlorinated hydrocarbons, such as butyrolactone, dimethylformamide, methanol, dioxane, acetonitrile, methyl ethyl ketone, nitrobenzene, dimethylsulphoxide, benzonitrile or 2- nitrochlorobenzene.

To manufacture such solutions, the dyestuffs according to the invention, in the form of the free bases or as salts of organic acids with 4 30 carbon atoms, are stirred with chlorinated hydrocarbons and monobasic organic acids with 4 30 carbon atoms, optionally with the addition of polar organic solvents which are completely miscible with chlorinated hydrocarbons, and optionally at elevated temperature.

in the examples, the relationship of parts by weight to parts by volume is as of a gram to a millilitre.

ILLUSTRATlVE EXAMPLE A This example illustrates the preparation of a representative 9a-methyl-2,3,9,Qa-tetrahydro-oxazo-I 3 ,2a

indole of the formula I and corresponds to Example 1 of German Patent application JP 20 614.8, filed Dec. 9, 1970. The preparation of other compounds of the formula I is shown in German Patent Application P 20 60 614.8. A certified copy of the German Application and a translation thereof are part of the file hereof.

EXAMPLE 1 CH3 N o H c cu which crystallizes to give a colorless substance of melting point: 44 46.

Analysis:

C H N 0 Calculated: 76.8 8.4 6.9 7.9 Found: 76.1 8 6 6.9 8.2

EXAMPLE 1 25.5 g of dimethylformamide are added dropwise over the course of /2 hour at 30 35C to 40.5 g of phosphorus oxychloride, the mixture is then stirred for a further /2 hour at 45 50C, and 6 g of acetonitrile are subsequently added. 45 g of 9,9,9a-trimethyl- 2,3,9,9a-tetrahydro-oxazolo-[3,2a]-indole are then added over the course of 2 hours, whilst keeping the temperature at between 50 and 55C, and the mixture is subsequently stirred for a further 18 hours at 50C. It is then stirred into 400 g of ice/water and rendered alkaline with 20% strength sodium hydroxide solution, in the course of which the temperature should not exceed 10C, and the whole is stirred for a further 5 hours at this temperature and then for a further 15 hours at room temperature, in the course of which the crude product initially obtained as an oil gradually solidifies. Crude yield: 41.5 g.

The crude product can be further purified by redissolving in cyclohexane and precipitating at 0C. Colourless crystals, which assume a violet colour on the surface after prolonged standing; melting point: 74 76C.

Analysis: C

g of dimethylformamide are added dropwise over the course of /2. hour at 40 50C to 27 g of phosphorus oxychloride, the mixture is then stirred for a further hour at 50 60C, and 4 g of acetonitrile are added. Thereafter, 45 g of 2-phenoxymethyl-9,9,9a-trimethyl- 2,3,9,9a-tetrahydro-oxazolo[3,2al-indole are added in portions over the course of 2 hours and the whole is then stirred for a further 150 hours at 50C. The reac tion product which precipitates after introducing the mixture into ammoniacal ammonium chloride solution is recrystallised from isopropanol with the addition of charcoal and is obtained in good yields. Melting point: 1 14 1 17C. Constitution:

EXAMPLE 3 7.8 g of dimethylformamide are added over the course of V2 hour at 40 50C to 14 g of phosphorus oxychloride, the mixture is then stirred for a further /2 hour at 50 60C and 2 g of acetonitrile are added. 16.2 g of 7methoxy-9,9,9a-trimethyl-2,3,9,9a-tetrahydro-oxazolo-[3,2a1-indo1e are then added dropwise at 50 60C over the course of 1 hour, the reaction mixture is subsequently stirred for a further 15 hours at 50C and then poured into ammoniacal ammonium chloride solution, and the whole is first stirred for 2 hours at 0C and then, after addition of 150 ml of strength NaOH, for a further 12 hours at room temperature. The crude product which precipitates is recrystallised from methanol with the addition of charcoal. Melting point: 107 109C. Constitution:

2.5 g of 1-(2'-chloroethyl)-2-(formylmethylene)-3,3- dimethy1-2,3-dihydroindole are stirred with 1.5 g of N- diethylaniline in 20 ml of chlorobenzene and 1.5 g of phosphorus oxychloride for 2 hours at 70C. The sol- .vents are stripped off in steam and the residue is poured into 5% strength sodium chloride solution with stirring. The crude dyestuff which precipitates is recrystallised from 5% strength sodium chloride solution. It corresponds to the formula and dyes materials of polyacrylonitrile in violet shades.

EXAMPLE 5 1.6 g of N-phenyl-morpholine and 2.4 g of 1-(2- chloroethyl)-2-formylmethylene-3,3-dimethyl-2,3- dihydroindole in 200ml of glacial acetic acid are stirred for 10 hours at C. The reaction mixture is poured into ml of 20% strength sodium chloride solution with stirring, and the dyestuff which separates out is separated off and dried in vacuo at 60C. The dyestuff corresponds to the formula and dyes materials of polyacrylonitrile in red-violet shades.

EXAMPLE 6 2.5 g of 1-(2-chloroethyl)-2-(formylmethylene)-3,3- dimethyl-2,3-dihydroindole are stirred with 2.3 g of 4- ethoxy-N-methyl-diphenylamine in 20 m1 of chlorobenzene and 1.5 g of phosphorus oxychloride for 2 hours at 70C. The solvents are stripped off in steam and the residue is poured into 5% strength sodium chloride solution with stirring. The crude dyestuff which precipitates is purified by reprecipitation from water/5% strength sodium chloride solution. it corresponds to the formula and dyes materials of polyacrylonitrile in violet shades EXAMPLE 7 2.2 g of l-methyll ,2,3,4-tetrahydro-quinoline are stirred with 3.7 g of 1-(2-chloroethyl)-2- formylmethylene-3.3-dimethyl-2,3-dihydroindole in 30 ml of glacial acetic acid for 8 hours at 100C. The reaction mixture is poured into ml of 20% strength sodium chloride solution with stirring and the product is purified by rcprecipitation from water/sodium chloride solution and is dried at 60C in vacuo. The dyestuff corresponds to the formula and dyes materials of polyacrylonitrile in red-violet shades.

If one of the instructions indicated in Examples 4, 5, 6 or 7 is followed, dyestuffs are obtained which dye materials of polyacrylonitrile in the colour shades indicated in Table 1.

Table l Aldehyde Component (H-acid Component Colour shade l4 2'-ehlorocthyl )-2-(forniyl methylene )-3,3-dimethyl 2 3- dihydroindolc N-dimcthyl-uniline N( mcthylB-chloroethyl )-aniline N-(CthyLB-chloroethyl )-uniline N-(di-B-ehloroethyl)-aniline N4 methyl-cyanoethyl )-unilinc an i l i no N-( mcthyl-cyclohexyl )-aniline N-(cthyl'B-chloroethylJ-3-mcthylaniline N-(di-n-propyl )-aniline N-( n-hutyI-B-chloroethyl )-zmiline N-(n-hutyl-Bhydroxyethyll-aniline ethyl-( Z-dimethylaminocthyl )-aniline N-dimethyl-o-toluidine N dimcthyl-m-toluidine N-(ethyl-hcnzyU-aniline N-phenyl-morpholine Nmethyl-diphenylamine Nethyl-diphenylamine Nmcthyl2methyl4'-ethoxydiphenylaminc 4ethoxy-diphenylumine 4-methyl-diphcnylamine N-ethyl-carhazole l .2.3,4-tctmhydro-9-methylearbazolc carhazole N-mcthyl-eurhuzolc N-propylearhzlzole N-( methyl )-B-hydroxyethyl )-anilinc N-(methyl-cyanoethyl )-3-methyl N-methyl-4-ethoxy-diphenylamine N-methyl-4-mcthoxy-diphenylamine N-ethyl-4-ethoxy-diphcnylaminc N-mcthyl-4-methyl-diphcnylaminc 2-nitro-4-methyl-diphenylaminc 3-acctumino-Q-methyl-earbuzole bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red hluish-tingcd red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red bluish-tinged red hluishtinged red bluish-tinged red violet bluish-tinged red bluish-tinged red violet violet hluish tingcd rcd violet bluish-tinged red violet violet bluish-tinged red bluish-tinged red yellowish-tinged red bluish-tinged red bluish-tinged red red yellowish-tinged red yellowish-tinged red EXAMPLE 8 2.3 g of l-(2'-chloroethyl)-2-(formylmethylene)-3,3- dimethyl-Z,3-dihydroindole are reacted with 2.0 g of 65 Z-phenylindole in 30 ml of glacial acetic acid, after addition of 1 ml of acetic anhydride, for 2 hours at 80C and dyes materials of polyacrylonitrile in scarlet-red shades of good fastness to light.

On following the same procedure and reacting the aldehydes listed in Table 2 with the amine components listed, dyestuffs are obtained which dye materials of polyacrylonitrile in the shades indicated:

Table 2 Continued Aldehyde Component lndole Component Colour shade l( 2-ehloroethyl )-2-( formylmethylene )-5 carboethoxy-3 ,3- (methyl-2,3-dihydroindolc red-orange red-orange l-methyl 5-methoxy-2-phenylindole Z-phenylindole l-methyl-2-phenylindolc l-methyl-5-methoxy-2-phe nylindole red-orange red-orange 7-cthylindole orange l-ethyl-2-methyl-(yJ-hcnzoindole violet 2-phenyl-7-ethylindole orange J, 5 CH I- s EXAMPLE 9 CCH;, H C

dimethyl-2,3-dihydroindo1e and 1.7 g of 1,3,3- 20 trimethyl-2-methylene-2,3-dihydroindole in 20 ml of glacial acetic acid are warmed to 80C for 4 hours and the reaction mixture is then introduced into 200 ml of shades 20% strength sodium chloride solution. the dyestuff o f n i the same procudure, the Starting Wl'llCl'l has separated out after stirring for several hOUI'S 2S ponents listed yield dyestuffs which dye m ner-i 15 of is Separated Off and dried in Vacuo at The y polyacrylonitrile in the colour shades indicated in stuff corresponds to the formula Table 3;

and dyes materials of polyacrylonitrile in red-violet Table 3 Aldehyde Component Methylene Component Colour shade l-(2'-chloroethyl )-2(formyll,3.Il-trimcthyl-S-ehloro-2-methylenebluish-tinged red methylene )-3.3-dimetl1yl- 2.3-tlih 'droindule 'lv3-dihydroindole v l,3.3.5-tetramethyl-Z-methylene-Z.3-

l-( 2'-chloro-n-propyl-2- (formylmethylene )3.3- dimeth vl-2.3-dihydroindole methylene )-3.3-dimethyl-5methoxy- 2,3-dihydroindole l 2'-ehloroethyl )-2-(formy| methylene )-3.3'dimethyl-5- methyl-2.3-dihydroindole 'hydroindole .3 3-trimethyl 5-methoxyQ-methylcnc- .B-dihydroindole l 3.. -trimethyl-5-nitro-Z-methylene 2.3-dihydroindole l ,3.3-trimethyl-5-ethoxy-2-methylene- 2,3-dihydroindole l ,3.S-trimethyl-S-trifluoromcthyl-Z- mcthylene-lIl-dihydroindole l .3 3-trimethyl-5-ucetz1mino-2- methyleneJZ.3-dihydroindole l 3.3-trimcthyl-5-ezlrhomethoxy2- 'methylene-lidihydroindole l3.3trimethyl-5-chloro-2-methylene- 2,3-dihyd roindolc l 3,3-trimethyl-5-methoxy-2-methylene- 2,3-dihydroindole l.3.3-trimcthyl-2-melhylene-2.3- dihydroindole l,3 3-trimethyl-Z-methylene-S-chlorti 2,3-dihydroindole L3 3-trimethyl2-methylene-S-curbw methoxy-2 3-dihydroindole l.3,3-trimethyl-2-methylene-2.3- dihydroindole bluish-linged red bluish-tinged red strongly bluishtinged red strongly bluishtinged red hluishtingcd red strongly bluishtinged red strongly hluishtinged red bluish-tinged red hluishtinged red bluish tinged red bluish-tinged red strongly bluish tinged red bluish-tinged red hluished-tinged red strongly bluishlinged rcd strongly bluishtinged red Strongly bluishtinged red strongly hluish tinged red bluish-tinged red EXAMPLE 10 CIHH 3.6 g of 1-( 2 '-chloro-3 '-phenoxy )-propyl-2- a H (formylmethylene)-3,3-dimethyl-2,3-dihydroindolc J- CH1 and 1.3 g of p-anisidine in 15 ml of glacial acetic acid N C1- are warmed to 80C for 1 hour. The reaction mixture CLHWCHZCI is introduced into 200 ml of 20% strength aqueous sodium chloride solution and stirred for 15 hours, and the crude product which has precipitated is then purified by rcprecipitation from 2.4% strength aqueous sodium chloride solution with the addition of charcoal. The dyestuff, which is obtained in reddish-yellow crystals, corresponds to the formula (a ena-en oand dyes materials of polyacrylonitrile in yellow shades of good fastness to light.

EXAMPLE 1 l 2.5 g of l-(2-chloroethyl)-2-(formylmethylene)-7- methoxy-3,3-dimethyl-2,3-dihydroindole and 1.2 g of p-toluidine in 20 ml of glacial acetic acid are reacted for 1 hour at 88C. The crude product which has precipitated after pouring the reaction mixture into 20% strength aqueous sodium chloride solution and stirring for 10 hours is purified by recrystallisation from 10% strength aqueous sodium chloride solution with the addition of charcoal. The dyestuff, which is obtained in yellow crystals, corresponds to the formula and dyes material of polyacrylonitrile in yellow shades of good fastness to light.

EXAMPLE 12 35 and dyes materials of polyacrylonitrile in yellow Shades of good fastness to light.

If the procedure indicated in Examples 10, l 1 or 12 is followed, the components listed in Table 4 yield dyestuffs having good fastness properties, which dye mate- 4 rials of polyacrylonitrile in the shades indicated:

Table 4 Amine Component Aldehyde Component Colour shade p-anisidine l-( T-chloroethyl )fl-(formylmethylene )-3,3- yellow dimethyl-2,3dihydroindole p-toluidine l-( 2-chloroethyl )-2-( formylmethylene )-3,3 yellow dimethyl-2,3-dihydroindole hexuhydroearhazole l( T-ehloroethyl )-2-(formylmethylcnc )-3 3 yellow dimethyl-2,3-dihydroindole 4-aminodiphenylmethnne l-(2ehlorocthyl) 2-(formylmethylene)-3,3- yellow dimethyl-2,3-dihydroindole 2,3-dimethyl-dihydroindole 1(2'-ehloroethyl)-2-(formylmethylene)-3,3- yellow 2,3-Llimethyll 2,3 4-tetrahydro-quinoxaline p-nnisidine 2-meth \'l-dihydroindole 2,3-dimethyll 2 3,4-te1rnhydroquinoxnline pannisidine p-toluidine Z-methyl-dihydroindole p-toluidine p-nnisidine Z-methyltlihydroindole p-toluitline dimethyl-2,3-dihydroindole l-( 2 -chloroeth \'l )-2 formylmethylenc )-3 3- reddish-tinged dimethyl-Z,fl-dihydroindole yellow l-( 2'-ehloroethyl )-2-( formylmethylene )-3,3 yellow Alimethyl-S-methoxy-ZJ-dihydroindole l-( 2-ehloroethyl )-2-(formylmcthylene )-3,3 yellow dimethyl-5-methoxy-2,3-dihydroindole l( 2 -ehloroeth l )-2-( formylmethylenc )-3,3- reddish-tinged dimethyl-5-eyuno-2,3-dihydmindole R and R conjointly form a S-membered or 6- 4. Dyestuff of claim 1 in which one of R and R is membered ring and represent a trimethylene or tethydrogen and the other is methyl. ramethylene bridge or a trimethylene or tetrameth- 5. A basic dyestuff of the formula ylene bridge substituted by methyl, ethyl, n-propyl, methoxy or ethoxy; and 5 Z is a single C-C bond, O, -S,methylene,

ethylidene, NH, N-CH N-C l-l N-n-C H C CH:x or N-n-C -H l 2. Dyestuff of claim 1 in which R; and R are both hydrogen. 10 Cl 3. Dyestuff of claim 1 in which one of R and R is CH2 CHZC' hydrogen and the other is methyl, chloromethyl, Hnc H phenyl, phenoxymethyl, methoxymethyl, allyloxymethyl, or n-hexoxymethyl. l 5 

1. DYESTUFF OF THE FORMULA
 2. Dyestuff of claim 1 in which R4'' and R5'' are both hydrogen.
 3. Dyestuff of claim 1 in which one of R4'' and R5'' is hydrogen and the other is methyl, chloromethyl, phenyl, phenoxymethyl, methoxymethyl, allyloxymethyl, or n-hexoxymethyl.
 4. Dyestuff of claim 1 in which one of R4'' and R5'' is hydrogen and the other is methyl.
 5. A basic dyestuff of the formula 